Photocatalytic Splitting of CS2 to S8 and a Carbon–Sulfur Polymer Catalyzed by a Bimetallic Ruthenium(II) Compound with a Tertiary Amine Binding Site: Toward Photocatalytic Splitting of CO2?

The catalytic photocleavage of CS2 to S8 and a (CxSy)n polymer with visible light using a dinuclear ruthenium(II) compound with a bipyridine units for photoactivity and a vicinal tertiary amine binding site for CS2 activation was studied. The catalyst was characterized by X-ray diffraction, 1H NMR, and 13C NMR, ESI-MS and elemental analysis. CS2 photocleavage was significant (240 turnovers, 20 h) to yield isolable S8 and a (CxSy)n polymer. A mononuclear catalyst or one without an amine binding site showed significantly less activity. XPS of the (CxSy)n polymer showed a carbon/sulfur ratio ∼1.5–1.6 indicating that in part both C–S bonds of CS2 had been cleaved. Catalyst was also included within the polymer. The absence of peaks in the 1H NMR verified the (CxSy)n nature of the polymer, while 13C NMR and IR indicated that the polymer had multiple types of C–S and C–C bonds.

本研究探讨了利用含有双吡啶单元的光活性位点和邻位叔胺键合位点的二核钌(II)化合物，在可见光照射下对二硫化碳进行催化光解，生成八硫环(S8)和(CxSy)n聚合物的过程。该催化剂通过X射线衍射、1H核磁共振、13C核磁共振、电喷雾电离质谱和元素分析进行了表征。二硫化碳的光解反应显著（转化次数达240次，反应时间20小时），成功生成了可分离的S8和(CxSy)n聚合物。单核催化剂或无胺键合位点的催化剂表现出显著较低的反应活性。(CxSy)n聚合物的X射线光电子能谱表明碳/硫比为约1.5–1.6，这表明二硫化碳中的部分C-S键已被断裂。催化剂也包含在聚合物中。1H核磁共振中峰的缺失验证了聚合物的(CxSy)n结构，而13C核磁共振和红外光谱则表明聚合物具有多种类型的C-S和C-C键。